US4977007A - Solid electrochemical element and production process therefor - Google Patents
Solid electrochemical element and production process therefor Download PDFInfo
- Publication number
- US4977007A US4977007A US07/097,367 US9736787A US4977007A US 4977007 A US4977007 A US 4977007A US 9736787 A US9736787 A US 9736787A US 4977007 A US4977007 A US 4977007A
- Authority
- US
- United States
- Prior art keywords
- solid electrolyte
- solid
- particles
- electrochemical element
- plastic resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000010949 copper Substances 0.000 description 9
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- 229910019540 RbCu4I1.5Cl3.5 Inorganic materials 0.000 description 5
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- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 3
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
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- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910008102 Li3 N Inorganic materials 0.000 description 1
- 229910008095 Li3 PO4 Inorganic materials 0.000 description 1
- 229910011626 Li4 SiO4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 229910000423 chromium oxide Inorganic materials 0.000 description 1
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- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 239000002001 electrolyte material Substances 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
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- 239000000155 melt Substances 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
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- 125000006850 spacer group Chemical group 0.000 description 1
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Images
Classifications
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
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- H01G11/22—Electrodes
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- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Definitions
- the present invention relates to a solid electrochemical element, which includes an ion conductor and the constituent members of which are all solid, such as a solid cell, a solid electrical double layer capacitor, a solid electrochromic display or the like, as well as to a process for producing said element.
- the present invention relates to a solid electrochemical element with excellent mechanical strength and excellent environmental resistance which is constituted by (a) an ion conductor comprised of a solid electrolyte and an insulating supporting substance, such as a plastic resin or the like, and having flexibility and excellent environment resistance, and (b) an electrode material in particulate form, as well as to a process for producing said element.
- Solid electrochemical elements whose constituent members are all solid are advantageous in that they have no problem of liquid leakage and they can be easily produced in a small and thin shapes.
- a solid ion conductor for moving ions within the element namely, a solid electrolyte.
- the solid electrolyte is classified by the type of movable ion, such as Li + -conductive solid electrolyte, Ag + -conductive solid electrolyte, Cu + -conductive solid electrolyte, H + -conductive solid electrolyte, etc.
- a solid electrochemical element is constituted by combining one of these solid electrolytes with an appropriate electrode material.
- a solid electrochemical element is ordinarily constituted by shaping a solid electrolyte powder into a layer by pressing or into a thin film by vapor deposition and providing a pair of electrodes on both surfaces of the layer or the thin film to form one solid electrochemical element per one solid electrolyte layer.
- the solid electrochemical elements when produced in a large and thin shape, generally tend to lack in elasticity and consequently are fragile to mechanical impacts and easily destroyed or impaired.
- the solid electrolyte generally comprises a chemically active monovalent cation as a conducting element.
- This monovalent cation when exposed to oxygen or moisture in the atmosphere, is converted to a divalent cation by oxidation or immobilized in the electrolyte crystal as an oxide, whereby the conducting function of the electrolyte is lost.
- each constituent element of the element group is connected in series or in parallel.
- the electrolyte used in each element generally has random ion conductivity and has no anisotropy
- each element must have an electrolyte layer ionically isolated from other electrolyte layers. Without this isolation, the ionic flow within the electrolyte of one element not only occurs between the electrodes of the element but also spreads into the electrodes of other elements, whereby the element group fails to exhibit its desired function.
- a flexible, environment-resistant ion conductor comprised of a solid electrolyte in particulate form and supporting substance which is an insulator and which surrounds the solid electrolyte, preferably comprised of a solid electrolyte in particulate form and a supporting substance which is a plastic.
- an ion conductor having an ion conductivity which is anisotropic by allowing the plastic resin to have a thickness which is approximately the same as the particle diameter of the solid electrolyte particles or by alternately stacking layers of a sheet of a solid electrolyte and a sheet of a supporting substance for the solid electrolyte, such as a plastic resin or the like and cutting the resulting laminate in the thickness direction.
- Such an ion conductor is produced by a process including a step of crushing solid electrolyte particles by pressing.
- solid electrolyte particles and a plastic resin powder or grains are mixed in with a solvent or under heating and the mixture or its melt is shaped by rolling to obtain an ion conductor in sheet form.
- a solid electrochemical element with flexibility and environmental resistance by surrounding solid electrolyte particles and electrode material particles with a plastic resin.
- This solid electrochemical element is produced by separately or jointly mixing solid electrolyte particles and electrode material particles with a plastic resin in a solvent or hot mixing these particles directly with a plastic resin powder or grains to obtain particles coated with said plastic resin, and separately shaping these coated particles to produce a shaped material of coated solid electrolyte particles and a shaped material of coated electrode material, followed by joining; or jointly shaping these two coated materials into one integral body.
- the solid electrochemical element is produced by a process including a step of crushing solid electrolyte particles by pressing.
- FIG. 1 is a schematic view showing the structure of an embodiment of the ion conductor of the present invention.
- FIG. 1A is a schematic top plan view and
- FIG. 1B is a schematic sectional side elevational view.
- solid electrolyte particles 1 are surrounded by a supporting substance 2 for supporting the solid electrolyte particles 1, except for the upper and lower surfaces thereof which are exposed as is necessary for the formation of an ion-conductive path.
- FIG. 2 is a schematic representation of the steps for producing an ion conductor according to the present invention.
- a mixture 4 consisting of solid electrolyte particles 1, a supporting substance 2 for the solid electrolyte particles 1 and a solvent is applied by screen-printing onto a substrate 3 with a spatula 6 in FIG 2A, dried and then rolled by rollers 7 and 8 in FIG. 2C, whereby an ion conductor is produced.
- FIG. 3 is an isometric cutaway view showing the structure of an ion conductor having ion conductivity which is anisotropic and which is obtained by solid electrolyte and a sheet of a supporting substance for the solid electrolyte, such as a plastic resin or the like (FIG. 3A), and then cutting the resulting laminate along line B of FIG. 3A (FIG. 3B).
- a plastic resin or the like such as a plastic resin or the like
- FIG. 4 shows four views (FIGS. 4A-4D) of the structure of a laminated film battery using an ion conductor.
- the ion conductor or solid electrochemical element including an ion conductor of the present invention uses a foreign substance, namely, an insulating material, which supports and surrounds a solid electrolyte. That is, the solid electrolyte material or the electrode material is surrounded by an insulating supporting material for the solid electrolyte, preferably a plastic resin material, except for the portions thereof, respectively which form an ion- or electron-conductive path, optionally having a particular directionality.
- the insulating, supporting substance for the solid electrolyte is pushed into the gaps between the solid electrolyte particles or between the electrode material particles in forming an ion conductor (a shaped material of solid electrolyte) or a shaped electrode material or in assembling a solid electrochemical element, whereby an aggregate of particles is formed in which the neighbouring particles are in direct contact with one another and each particle is surrounded by the insulating, supporting substance for the solid electrolyte.
- the particles, as constituent members of the ion conductor, the electrode or the solid electrochemical element are given an aggregate shape, can secure an electrical and ionic contact, and are not directly exposed to oxygen and moisture in the air so that they are less likely to undergo deterioration.
- a sheet-type ion conductor (a shaped material of solid electrolyte) with flexibility and excellent ion conductivity, as well as a shaped electrode material, and, as a result, there can be obtained a solid electrochemical element having excellent mechanical strength and excellent environmental resistance, and which is capable of generating a large current.
- the ion conductor of the present invention can also be formed in a sheet shape wherein surfaces of solid electrolyte particles are coated with an insulating supporting substance for the solid electrolyte (e.g., a plastic resin) except for particular surfaces, for example, upper and lower surfaces thereof.
- an insulating supporting substance for the solid electrolyte e.g., a plastic resin
- the electrodes cover and contact the upper and lower surfaces of the solid electrolyte particles which are not coated with the insulating supporting substance and, thus, the electrodes and the ion conductor are connected ionically.
- the ions do not move in the lateral direction but only in the vertical direction of the sheet, whereby no ionic flow occurs between two neighbouring electrodes or between two neighbouring but opposing electrodes.
- a solid electrochemical element group consisting of a plurality of solid electrochemical elements which are electrically independent from one another, by providing two or more pairs of opposing electrodes on the two opposing surfaces of an ion conductor sheet.
- an ion conductor consisting of solid electrolyte particles coated with an insulating supporting substance for the solid electrolyte.
- this ion conductor is used in a solid electrochemical element, upper and lower surfaces of the ion conductor are provided with electrodes. Therefore, the ion conductor may be produced in such a manner that the upper and lower surface on which electrodes are to be provided, may be coated very thinly or may not be coated substantially with an insulating supporting substance for the solid electrolyte in order to obtain a good ionic contact between the ion conductor and the electrodes.
- the insulating supporting substance for the solid electrolyte according to the present invention can be any substance as long as it can surround the solid electrolyte particles and can form a flexible aggregate of the solid electrolyte particles.
- a plastic resin is preferred.
- the plastic resin there can be preferably used those which can be stably mixed with a solid electrolyte containing a high concentration of a chemically active monovalent cation such as Na + , Li + , Ag + , Cu + , H + or the like, or with an electrode material, as a strong oxidizing agent or a strong reducing agent.
- plastic resins include, for example, polyethylene, polypropylene, synthetic rubbers (e.g., styrene-butadiene rubber, Neoprene rubber), silicone resins, acrylic resins, etc.
- the fine powder of the resin is dry-blended with solid electrolyte powder or grains, or with electrode material powder or grains.
- the particle diameter of the resin preferably ranges from 1/10 to 1/10,000 times the particle diameter of each powder particulate or grain.
- the particles of polyethylene, polypropylene or acrylic resin coat the surface of each particle of the solid electrolyte owing to the static electricity generated between the respective particles.
- a synthetic rubber such as styrene-butadiene rubber, Neoprene rubber or the like
- a silicone resin or an acrylic resin is used
- wet blending is conducted using an organic solvent, such as toluene, xylene or the like.
- a synthetic rubber, an acrylic resin or a silicone resin is dissolved in an organic solvent in an amount ranging from 5 to 20% by weight; to the solution is added a solid electrolyte powder or grains, or an electrode material powder or grains; they are mixed and dispersed to obtain a slurry; the slurry is cast on a TEFLON sheet; and the solvent is removed under vacuum, if necessary with heating, whereby a shaped body can be obtained.
- the slurry itself can be treated under vaccum to remove the solvent and then shaped by pressing.
- the solid electrolyte used in the present invention includes Li + -conductive solid electrolytes, such as LiI, LiI.H 2 O, Li 3 N, Li 4 SiO 4 -Li 3 -Li 3 PO 4 , polyethylene oxide-LiCF 3 SO 3 and the like; Ag + -conductive solid electrolytes, such as RbAg 4 I 5 , Ag 3 SI, AgI-Ag 2 O-MoO 3 glass and the like; Cu + -conductive solid electrolytes, such as RbCu 4 I 1 .5 Cl 3 .5, RbCu 4 I 1 .25 Cl 3 .75, K 0 .2 Rb 0 .8 Cu 4 I 1 .5 Cl 3 .5, CuI-Cu 2 O-MoO 3 glass and the like; H + -conductive solid electrolytes, such as H 3 Mo 12 PO 40 .29H 2 O, H 3 W 12 PO 40 .H 2 O and the like; and Na + -conductive solid electrolytes represented by Na- ⁇ -Al 2
- the electrode material of the present invention there can be used, for example, carbon materials, such as graphite, acetylene black, active carbon and the like; sulfides, such as titanium sulfide, niobium sulfide, cuprous sulfide, silver sulfide, lead sulfide, iron sulfide and the like; oxides, such as tungsten oxide, vanadium oxide, chromium oxide, molybdenum oxide, titanium oxide, iron oxide, silver oxide, copper oxide and the like; halides, such as silver chloride, lead iodide, cuprous iodide and the like; and metal materials, such as copper, silver, lithium, gold, platinum, titanium and their alloys.
- carbon materials such as graphite, acetylene black, active carbon and the like
- sulfides such as titanium sulfide, niobium sulfide, cuprous sulfide, silver sulfide, lead
- a solid electrolyte cell or battery can be constituted by combining an ion conductor (a shaped material of solid electrolyte particles) and an electrode material which can give ions to the ion conductor or receive ions therefrom, such as titanium disulfide or the like.
- an ion conductor a shaped material of solid electrolyte particles
- an electrode material which can give ions to the ion conductor or receive ions therefrom, such as titanium disulfide or the like.
- a solid electrochemical display element (a solid electrochromic display) can be constituted by using an ion conductor and an electrode material which can give or receive ions and simultaneosuly cause an optical change, such as tungsten oxide or the like.
- a solid electrical double layer capacitor can be constituted by using an ion conductor and an electrode material which does not give or receive ions but which can form an electrical double layer at the interface with the ion conductor, such as active carbon or the like.
- a solid electrolyte for example, a powder of RbCu 4 I 1 .5 Cl 3 .5 100% of which passes through a 200 mesh, is dispersed in a toluene solution of a styrene-butadiene copolymer so that the volume fraction of the powder after drying, becomes 85%.
- the resulting slurry is spread on a TEFLON sheet using an applicator bar and placed in dry air to remove the toluene, whereby a flexible sheet-type ion conductor (a shaped material of solid electrolyte particles) having no fluidity is obtained.
- This ion conductor can be used as it is for constitution of a solid electrochemical element but, by rolling it with a roller press so as to have a thickness of about 2/3 or less of the original thickness, can be made into a sheet-type ion conductor with improved ion conductivity wherein the solid electrolyte particles have been crushed by pressing.
- a shaped electrode can also be formed in a similar manner.
- a copper powder having particle diameters of 5 microns or less and a RbCu 4 I 1 .5 Cl 3 .5 powder having particle diameters 100% of which pass through a 200 mesh are mixed in a weight ratio of 90:10.
- the mixed powder is dispersed in a toluene solution of a styrene-butadiene copolymer so that the volume fraction of the mixed powder after drying becomes 90%.
- the resulting slurry is spread on a TEFLON sheet using an applicator bar and placed in dry air to remove the toluene, whereby a flexible sheet-type shaped electrode material is obtained. It can be rolled by a roller press to have a thickness of about 2/3 or less of the original thickness, whereby an electrode having an excellent electrical conductivity and an excellent ionic conductivity can be obtained.
- Production of a solid electrochemical element can be conducted as above by making a shaped ion conductor and a shaped electrode material into one integral body. Alternatively, it can be conducted by directly shaping the respective powders or grains coated with a plastic resin into one integral body.
- FIG. 1 shows the structure of an ion conductor according to the present invention.
- FIG. 1(A) is a plan view of the ion conductor and
- FIG. 1(B) is a sectional view obtained by cutting the ion conductor of FIG. 1(A) at line C.
- 1 is a solid electrolyte in particulate form and 2 is a supporting substance for the solid electrolyte 1 which is an insulator.
- the slanted line portions of solid electrolyte 1 in FIG. 1A are the portions of the particulate solid electrolyte hidden, i.e., covered, by the insulating supporting substance 2 for the solid electrolyte 1.
- RbCu 4 I 1 .5 Cl 3 .5 as a particulate solid electrolyte was ground with a ball mill under dry air, and only the sieve portion of solid electrolyte having particle diameters of 80 to 100 microns was used.
- a silicone rubber was used as the supporting substance for the solid electrolyte.
- Preparation of an ion conductor was conducted according the schematic process of FIG. 2. Firstly, the above two materials were mixed at a ratio of 1:1 by weight. Mixing was conducted thoroughly using toluene as a solvent for the silicone rubber in order to sufficiently disperse the particulate solid electrolyte in the silicone rubber.
- the resulting mixture 4 was screen-printed onto a stainless steel substrate 3 with a spatula 6 through a stainless steel screen 5 of 100 mesh [see FIG. 2(A)]. Then, the toluene was evaporated [see FIG. 2(B)]. Subsequently, the particulate solid electrolyte supported by the silicone rubber was rolled together with a silicone rubber 9 between two rollers 7 and 8 whose gap had been adjusted to 100 microns to obtain an ion conductor sheet having a thickness of 100 microns [see FIG. 2(C)]. This ion conductor sheet showed anisotropy with respect to ion conductivity. The ion conductivity at 25° C. was 4.5 ⁇ 10 -2 ⁇ -1 cm -1 in the thickness direction and 7.3 ⁇ 10 31 12 ⁇ -1 cm -1 in the lateral direction.
- ion conductors were prepared in the same manner as in Example 1. Each ion conductor showed anisotropy with respect to ion conductivity. The results are shown in Table 1.
- NASICON Na-super ion conductor
- a Na + -conductive solid electrolyte represented by Na 1+x Zr 2 P 3-x Si x O 12 (0 ⁇ x ⁇ 3) was ground so as to have particle diameters of 100 ⁇ 10 microns, and these particles were used as a particulate solid electrolyte.
- a polyethylene powder having a particle diameter of 100 microns was used as a supporting substance for the solid electrolyte.
- the particulate solid electrolyte and the polyethylene powder were mixed; the mixture was melted at 200° C.; and the melt was rolled between hot rollers whose gap had been adjusted to 100 microns to obtain a sheet.
- the temperature of the hot rollers was set at 30° C.
- the sheet had ion conductivities of 7.3 ⁇ 10 -5 ⁇ -1 cm -1 in the thickness direction and 2.6 ⁇ 10 -13 ⁇ -1 cm 31 1 in the lateral direction. By melting, the polyethylene could effectively surround each solid electrolyte particle.
- An ion conductor sheet was prepared in the same manner as in Example 5 except that the polyethylene as a supporting substance for the solid electrolyte was changed to a polypropylene resin.
- the sheet had ion conductivities of 5.4 ⁇ 10 -5 ⁇ -1 cm -1 in the thickness direction and 2.1 ⁇ 10 -13 ⁇ -1 cm -1 in the lateral direction.
- FIG. 3 Another embodiment of an ion conductor according to the present invention is shown in FIG. 3.
- the sheet was prepared by mixing LiCF 3 SO 3 and a PEO having a molecular weight of 750,000, dissolving the mixture in acetonitrile, casting the solution on a stainless steel plate, and evaporating the solvent at 70° C.
- a sheet 11 of the PEO alone was prepared in a similar manner.
- the two sheets were stacked alternatively [see FIG. 3(A)], and the laminate was cut at line B to prepare a zebra-patterned sheet [see FIG.
- the sheet was measured for ion conductivities between surfaces a, b and c. Ion conductivity was 3.4 ⁇ 10 -6 ⁇ -1 cm -1 between surfaces a and b and 7.1 ⁇ 10 -13 ⁇ -1 cm 31 1 between surfaces b and c.
- An ion conductor sheet was prepared in the same manner as in Example 1 except that 60% by weight of white, insulating particles of TiO 2 (70 microns in particle diameter) had been added to the silicone rubber of Example 1.
- the sheet had ion conductivities of 5.7 ⁇ 10 -1 ⁇ -1 cm -1 in the thickness direction and 2.2 ⁇ 10 -13 ⁇ -1 cm -1 in the lateral direction.
- a laminate-type thin film battery was prepared using an ion conductor prepared as described above. The preparation process is shown in FIG. 4.
- a positive electrode group of the battery is shown in FIG. 4(A) and a negative electrode group is shown in FIG. 4(B).
- the positive electrode group was prepared by vapor-depositing stainless steel on a glass substrate through a mask to form stainless steel portions 13, 15 and 17 and then vapor-depositing thereon CuI through a mask to form CuI portions 14 in a thickness of 3,000 ⁇ [see FIG. 4(A)].
- the portions 15 and 17 later become a positive electrode terminal and a negative electrode terminal, respectively.
- the negative electrode group was prepared by vapor-depositing stainless steel on a glass substrate 12 through a mask to form stainless steel portions 13 and then vapor-depositing thereon copper through a mask to form copper portions 16 [see FIG. 4(B)].
- the above-mentioned ion conductor sheet consisting of a particulate solid electrolyte 1 and a supporting substance 2 for the solid electrolyte 1 was put between the positive electrode group and the negative electrode group so that the electrode groups faced each other, and the circumference of the resulting laminate was coated with an epoxy adhesive 18, whereby a battery was prepared [see FIG. 4(D)].
- the connection of the respective electrode groups was accomplished using indium metal 19.
- the resulting battery was measured for electromotive force, and a voltage of 1.8 V existed between positive electrode terminal 15 and negative electrode terminal 17. Since the electromotive force of this battery was 0.6 V per single cell, it was found that the use of an ion conductor sheet according to this invention makes it unnecessary to divide the electrolyte into single cell portions. Further, in order to examine an effect when a plastic supporting substance for the solid electrolyte is used, a battery was constituted by using, as a substrate 12 for each electrode group, a polyimide film having a thickness of 0.4 mm. As a result, it was found that the battery had an excellent elasticity. Therefore, this battery was found to be suitable for use as an electric source for IC cards requiring elasticity.
- the ion conductor sheet containing insulating particles, prepared in Example 8 when put between transparent electrodes, produced a sharp pink color on a white background due to the precipitation of copper when a voltage was applied between the transparent electrodes and accordingly is suitable for use as an electrolyte for an electrochromic display.
- a powder of 5 microns or less as particulate solid electrolyte was sufficiently mixed with a toluene solution containing 10% of a styrene-butadiene copolymer, in a volume ratio of 85 (solid electrolyte) to 15 (copolymer).
- a suitable amount of toluene was used as a diluent.
- the mixture thus prepared was a slurry having a slight fluidity.
- the slurry was extended on a TEFLON sheet in a thickness of 100 microns using an applicator bar.
- Toluene was evaporated in dry air and then the dried film was rolled into a film thickness of 70 microns using a roller press to crush the solid electrolyte particles, whereby a desired ion conductor was obtained.
- the ion conductor was cut into specimen of 1 cm 2 .
- two copper electrodes each having the same size as the specimen, in a sandwich form. This was done by wetting the ion conductor surfaces with toluene and then pressing the cooper electrodes thereon. Subsequently, an AC having a voltage of 10 mV and a frequency of 1 KHz was applied between the two electrodes and the resulting AC resistance was measured. It was 1.5 ⁇ 10 -4 S/cm 2 .
- an ion conductor sheet was prepared according to the following.
- a particulate solid electrolyte there was used a powder having particle diameters of 1 micron or less which was difficult to crush by rolling, and an ion conductor sheet was prepared in the same manner as in Example 9.
- the resulting ion conductor showed a low ion conductivity of 9.5 ⁇ 10 -6 S/cm 2 .
- An ion conductor sheet was prepared in the same manner as in the sheet of Example 9 except that crushing and rolling was conducted using an ordinary press in place of the roller press. That is, the ion conductor sheet before crushing and rolling was sandwiched between two stainless steel plates (in the form of a square of 10 cm ⁇ 10 cm having a thickness of 1 cm) using spacers of 70 microns in thickness, and a pressure of 1 ton/cm 2 was applied by a press to crush the solid electrolyte particles. The resulting ion conductor sheet had an ion conductivity of 9.7 ⁇ 10 -5 S/cm 2 .
- roller pressing as compared with ordinary pressing by a press, can crush solid electrolyte particles more effectively and can provided an ion conductor with superior ion conductivity.
- a solid electrolyte namely, a powder of a Cu + -conductive solid electrolyte, represented by RbCu 4 I 1 .5 Cl 3 .5, having an average particle diameter of 10 microns was mixed with 20 parts by weight of a polyethylene powder having an average particle diameter of 0.1 micron in a dry nitrogen atmosphere.
- the mixture was formed into a shaped solid electrolyte material of 5 mm ⁇ 20 mm ⁇ 100 microns (thickness) using a roller press at a pressure of 200 kg/cm 2 .
- a shaped positive electrode material of 5 mm ⁇ 20 mm ⁇ 200 microns (thickness) consisting of 50 parts by weight of a powder of a positive electrode active substance represented by Cu 0 .1 NbS 2 , having an average particle diameter of 15 microns, 50 parts by weight of the above mentioned solid electrolyte powder and 15 parts by weight of the above mentioned polyethylene powder.
- a shaped negative electrode material of 5 mm ⁇ 20 mm ⁇ 120 microns (thickness) consisting of 50 parts by weight of a powder of a negative electrode active substance (metallic copper) having an average particle diameter of 8 microns, 50 parts by weight of the above mentioned solid electrolyte powder and 25 parts by weight of the above mentioned polyethylene powder.
- These shaped materials were stacked in three layers and a pressure of 250 kg/cm 2 was applied thereto, whereby a copper-type solid cell A was obtained as an integral body.
- a copper-type solid cell B was obtained in the same manner as in Example 10 except that a polypropylene powder having an average particle diameter of 0.1 micron was used in place of the polyethylene powder.
- a copper-type solid cell C was obtained in the same manner as in Example 10 except that no polyethylene powder was used.
- An Ag-type solid cell D was obtained in the same manner as in Example 10 except that there were used, as a solid electrolyte, a powder of an Ag + -conductive solid electrolyte represented by RbAg 4 I 5 , having an average particle diameter of 8 microns, as a positive electrode active substance, a powder of Ag 0 .1 NbS 2 having an average particle diameter of 15 microns, and as a negative electrode active substance, a powder of metallic silver having an average particle diameter of 8 microns.
- a solid electrolyte a powder of an Ag + -conductive solid electrolyte represented by RbAg 4 I 5 , having an average particle diameter of 8 microns, as a positive electrode active substance, a powder of Ag 0 .1 NbS 2 having an average particle diameter of 15 microns, and as a negative electrode active substance, a powder of metallic silver having an average particle diameter of 8 microns.
- An Ag-type solid cell E was obtained in the same manner as in Example 12 except that no polyethylene powder was used.
- a Li-type solid cell F was obtained in the same manner as in Example 10 except that there were used, as a solid electrolyte, a powder of a Li + -conductive solid electrolyte represented by LiI, having an average particle diameter of 15 microns, as a positive electrode active substance, a powder of WO 3 having an average particle diameter of 12 microns, and as a negative electrode active substance, a powder of Li 1 .5 WO 3 having an average particle diameter of 10 microns.
- a solid electrolyte a powder of a Li + -conductive solid electrolyte represented by LiI, having an average particle diameter of 15 microns, as a positive electrode active substance, a powder of WO 3 having an average particle diameter of 12 microns, and as a negative electrode active substance, a powder of Li 1 .5 WO 3 having an average particle diameter of 10 microns.
- a Li-type solid cell G was obtained in the same manner as in Example 13 except that no polyethylene powder was used.
- An H-type solid cell H was obtained in the same manner as in Example 10 except that there were used, as a solid electrolyte, a powder of a H + -conductive solid electrolyte represented by H 3 Mo 12 PO 40 .29H 2 O, having an average particle diameter of 20 microns, as a positive electrode active substance, a powder of WO 3 having an average particle diameter of 8 microns, and as a negative electrode active substance, a powder of HWO 3 having an average particle diameter of 8 microns, and the polyethylene powder was changed to an acrylic resin powder having an average particle diameter of 0.2 micron.
- a powder of a H + -conductive solid electrolyte represented by H 3 Mo 12 PO 40 .29H 2 O having an average particle diameter of 20 microns
- a powder of WO 3 having an average particle diameter of 8 microns
- the polyethylene powder was changed to an acrylic resin powder having an average particle diameter of 0.2 micron.
- An H-type solid cell I was obtained in the same manner as in Example 14 except that no acrylic resin powder was used.
- a solid electrolyte namely, a powder of a CU + -conductive solid electrolyte represented by RbCu 4 I 1 .25 Cl 3 .75, having an average particle diameter of 2 microns was mixed with 30 parts by weight of a toluene solution containing 10% by weight of a styrene-butadiene rubber to obtain a solid electrolyte slurry.
- the slurry was extended on a fluororesin plate using a bar coater in a thickness (when dried) of 20 microns and then dried for 3 hours at 50° C. under a reduced pressure of 1 Torr, whereby a solid electrolyte thin film of 60 mm (width) ⁇ 800 mm (length) ⁇ 20 microns (thickness) was obtained.
- the positive electrode thin film was provided on one surface of the solid electrolyte thin film and the negative electrode thin film was provided on the other surface of the solid electrolyte thin film. They were shaped into one integral body at a pressure of 20 kg/cm 2 using a roller press of 130° to 150° C. to obtain a thin film of 65 mm (width) ⁇ 1,000 mm (length) ⁇ 55 to 65 microns (thickness). This thin film was cut into pieces of 5 mm ⁇ 20 mm to obtain a solid cell J.
- a solid cell K was obtained in the same manner as in Example 15 except that the styrene-butadiene rubber was replaced by a silicone resin.
- a solid cell L was obtained in the same manner as in Example 15 except that the styrene-butadiene rubber was replaced by an acrylic resin.
- Example 15 On the two surfaces of a solid electrolyte film having a thickness of 20 microns, obtained in the same manner as in Example 15, were provided an electrode film having a thickness of 30 microns and consisting of a graphite powder, a solid electrolyte powder and a styrenebutadiene rubber, obtained in the same manner as in Example 15. They were shaped into one integral body at a pressure of 20 kg/cm 2 and at 130° to 150° C. using a roller press to obtain a sheet of 65 mm (width) ⁇ 1,000 mm (length) ⁇ 60 to 65 microns (thickness). The sheet was cut into pieces of 5 mm ⁇ 20 mm to obtain a solid electrical double layer capacitor M.
- a solid electrolyte namely, a powder of a H + -conductive solid electrolyte represented by H 3 Mo 12 PO 40 .29H 2 ), having an average particle diameter of 20 microns, 20 parts by weight of an acrylic resin powder having an average particle diameter of 0.2 micron and a graphite powder having an average particle diameter of 0.5 micron were mixed and shaped in the same manner as in Example 10 to prepare a graphite electrode of 5 mm ⁇ 20 mm ⁇ 30 microns (thickness).
- Three layers comprising in the following order (a) the above electrode, (b) a solid electrolyte film of 5 mm ⁇ 20 mm ⁇ 50 microns (thickness) consisting of a H + -conductive solid electrolyte and an acrylic resin and (c) a display electrode of 5 mm ⁇ 20 mm ⁇ 10 microns (thickness) containing tungsten trioxide (WO 3 ), prepared in the same manner as in Example 14 were pressed into one body, whereby a solid electrochromic display element N of 5 mm ⁇ 20 mm ⁇ 85 microns (thickness) was assembled.
- All of the solid electrochemical elements A, B, D, F, H, J, K, L, M and N according to the present invention withstand bending of several hundred times to several thousand times, and none of them showed a noticeable increase in internal resistance, when allowed to stand in the atmosphere. Meanwhile, the solid electrochemical elements C, E, G and I for comparison had no flexibility at all and were broken by bending one time and, when allowed to stand in the atmosphere, showed a significant increase in internal resistance.
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- Chemical Kinetics & Catalysis (AREA)
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- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
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- Electric Double-Layer Capacitors Or The Like (AREA)
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61-223101 | 1986-09-19 | ||
JP61223101A JPS6378405A (ja) | 1986-09-19 | 1986-09-19 | 異方性イオン伝導体 |
JP26340886 | 1986-11-05 | ||
JP61-263408 | 1986-11-05 | ||
JP62-72405 | 1987-03-26 | ||
JP62072405A JP2666276B2 (ja) | 1987-03-26 | 1987-03-26 | 固体電解質を含む電気化学素子部材の製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
US4977007A true US4977007A (en) | 1990-12-11 |
Family
ID=27300941
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/097,367 Expired - Lifetime US4977007A (en) | 1986-09-19 | 1987-09-08 | Solid electrochemical element and production process therefor |
Country Status (6)
Country | Link |
---|---|
US (1) | US4977007A (de) |
EP (1) | EP0260679B1 (de) |
KR (1) | KR900007731B1 (de) |
CN (1) | CN1022273C (de) |
CA (1) | CA1309456C (de) |
DE (1) | DE3785901T2 (de) |
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US5888672A (en) * | 1997-02-12 | 1999-03-30 | Gustafson; Scott D. | Polyimide battery |
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US6103359A (en) * | 1996-05-22 | 2000-08-15 | Jsr Corporation | Process and apparatus for manufacturing an anisotropic conductor sheet and a magnetic mold piece for the same |
US6131851A (en) * | 1998-06-02 | 2000-10-17 | Lockheed Martin Corporation | Apparatus having an energy generating skin as an outer covering |
US6379835B1 (en) | 1999-01-12 | 2002-04-30 | Morgan Adhesives Company | Method of making a thin film battery |
US6451480B1 (en) | 1999-10-18 | 2002-09-17 | Scott D. Gustafson | Polyimide-based lithium ion battery |
US6475678B1 (en) * | 1999-08-24 | 2002-11-05 | Japan Storage Battery Co., Ltd. | Nonaqueous electrolyte battery |
US6621212B1 (en) | 1999-12-20 | 2003-09-16 | Morgan Adhesives Company | Electroluminescent lamp structure |
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US8636876B2 (en) | 2004-12-08 | 2014-01-28 | R. Ernest Demaray | Deposition of LiCoO2 |
US8728285B2 (en) | 2003-05-23 | 2014-05-20 | Demaray, Llc | Transparent conductive oxides |
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US20140321030A1 (en) * | 2012-01-27 | 2014-10-30 | Tokyo Institute Of Technology | Solid ion capacitor and method for using solid ion capacitor |
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US20170162871A1 (en) * | 2014-07-04 | 2017-06-08 | Enocell Limited | Battery |
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US10531555B1 (en) * | 2016-03-22 | 2020-01-07 | The United States Of America As Represented By The Secretary Of The Army | Tungsten oxide thermal shield |
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Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4810599A (en) * | 1987-03-27 | 1989-03-07 | Japan Synthetic Rubber Co., Ltd. | Structure suitable for solid electrochemical elements |
US4828945A (en) * | 1987-03-27 | 1989-05-09 | Japan Synthetic Rubber Co., Ltd. | Solid electrolyte sheet and process for producing the same |
GB2205437B (en) * | 1987-04-30 | 1990-06-20 | Atomic Energy Authority Uk | Solid state electrochemical cell |
CN101889321A (zh) * | 2007-10-05 | 2010-11-17 | D·卡弗 | 高电容率低漏电的电容器和能量存储器件及其形成方法 |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4247499A (en) * | 1979-05-18 | 1981-01-27 | General Electric Company | Methods of forming a solid ion-conductive electrolyte |
US4517265A (en) * | 1982-06-30 | 1985-05-14 | Hydro-Quebec | Composite and flexible anodes for lithium cells in non-aqueous medium |
US4589197A (en) * | 1984-05-14 | 1986-05-20 | United Kingdom Atomic Energy Authority | Composite cathode for electrochemical cell |
US4614695A (en) * | 1983-03-14 | 1986-09-30 | Fanuc Ltd. | Battery and method of producing same |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2135858A5 (en) * | 1971-04-30 | 1972-12-22 | Comp Generale Electricite | Electrochemical cell - with catholytic electronic and/or ionic conductor consisting of copper sulphide or silver sulphide |
US3708729A (en) * | 1971-12-10 | 1973-01-02 | Unican Security Systems | Solid electrolyte films and devices containing same |
ZA785950B (en) * | 1978-10-23 | 1980-06-25 | South African Inventions | Electrochemical cell |
US4183988A (en) * | 1978-11-16 | 1980-01-15 | General Electric Company | Solid ion-conductive electrolyte |
JPS5795083A (en) * | 1980-12-05 | 1982-06-12 | Hitachi Maxell Ltd | Manufacture of solid electrolyte cell |
JPS57108831A (en) * | 1980-12-26 | 1982-07-07 | Hitachi Maxell Ltd | Manufacture of solid electrolytic thin plate |
DE3125525A1 (de) * | 1981-06-29 | 1983-01-20 | Varta Batterie Ag, 3000 Hannover | Festelektrolytkoerper |
DE3200757C1 (de) * | 1982-01-13 | 1983-07-21 | Fa. Carl Freudenberg, 6940 Weinheim | Flexible elektrolytische Zelle |
-
1987
- 1987-09-08 US US07/097,367 patent/US4977007A/en not_active Expired - Lifetime
- 1987-09-09 CA CA 546422 patent/CA1309456C/en not_active Expired - Lifetime
- 1987-09-16 EP EP19870113550 patent/EP0260679B1/de not_active Expired - Lifetime
- 1987-09-16 DE DE19873785901 patent/DE3785901T2/de not_active Expired - Fee Related
- 1987-09-18 CN CN87107102A patent/CN1022273C/zh not_active Expired - Fee Related
- 1987-09-18 KR KR1019870010356A patent/KR900007731B1/ko not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4247499A (en) * | 1979-05-18 | 1981-01-27 | General Electric Company | Methods of forming a solid ion-conductive electrolyte |
US4517265A (en) * | 1982-06-30 | 1985-05-14 | Hydro-Quebec | Composite and flexible anodes for lithium cells in non-aqueous medium |
US4614695A (en) * | 1983-03-14 | 1986-09-30 | Fanuc Ltd. | Battery and method of producing same |
US4589197A (en) * | 1984-05-14 | 1986-05-20 | United Kingdom Atomic Energy Authority | Composite cathode for electrochemical cell |
Cited By (71)
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US5154991A (en) * | 1991-06-10 | 1992-10-13 | The United States Of America As Represented By The Secretary Of The Army | Flexible solid electrolyte separator for use in a high temperature electrochemical cell, method of making the separator, and electrochemical cell including the separator |
US6103359A (en) * | 1996-05-22 | 2000-08-15 | Jsr Corporation | Process and apparatus for manufacturing an anisotropic conductor sheet and a magnetic mold piece for the same |
US5888672A (en) * | 1997-02-12 | 1999-03-30 | Gustafson; Scott D. | Polyimide battery |
US6131851A (en) * | 1998-06-02 | 2000-10-17 | Lockheed Martin Corporation | Apparatus having an energy generating skin as an outer covering |
EP0981176A1 (de) * | 1998-08-20 | 2000-02-23 | Sony Corporation | Festelektrolyt-Zelle |
US6423453B1 (en) | 1998-08-20 | 2002-07-23 | Sony Corporation | Solid electrolyte battery |
US6379835B1 (en) | 1999-01-12 | 2002-04-30 | Morgan Adhesives Company | Method of making a thin film battery |
US6475678B1 (en) * | 1999-08-24 | 2002-11-05 | Japan Storage Battery Co., Ltd. | Nonaqueous electrolyte battery |
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US20070171148A1 (en) * | 2006-01-13 | 2007-07-26 | Micheal Cassidy | Active matrix electrochromic display |
US7403319B2 (en) | 2006-01-13 | 2008-07-22 | Ntera Limited | Electrochromic device employing gel or solid polymers having specific channel direction for the conduction of ions |
WO2007082067A3 (en) * | 2006-01-13 | 2008-03-27 | Ntera Ltd | An electrochromic device employing gel or solid polymers having specific channel direction for the conduction of ions |
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US20140321030A1 (en) * | 2012-01-27 | 2014-10-30 | Tokyo Institute Of Technology | Solid ion capacitor and method for using solid ion capacitor |
US20140186719A1 (en) * | 2012-03-28 | 2014-07-03 | Sharp Laboratories Of America, Inc. | NASICON-Polymer Electrolyte Structure |
US9660241B2 (en) * | 2012-03-28 | 2017-05-23 | Sharp Laboratories Of America, Inc. | NASICON-polymer electrolyte structure |
US9502729B2 (en) | 2012-08-29 | 2016-11-22 | Corning Incorporated | Ion-conducting composite electrolyte comprising path-engineered particles |
US20140340821A1 (en) * | 2013-05-20 | 2014-11-20 | Tdk Corporation | Solid-state ion capacitor |
US9595399B2 (en) * | 2013-05-20 | 2017-03-14 | Tdk Corporation | Solid-state ion capacitor |
US10186386B2 (en) * | 2013-07-23 | 2019-01-22 | Murata Manufacturing Co., Ltd. | Solid ion capacitor |
US20160141115A1 (en) * | 2013-07-23 | 2016-05-19 | Murata Manufacturing Co., Ltd. | Solid ion capacitor |
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US20170162871A1 (en) * | 2014-07-04 | 2017-06-08 | Enocell Limited | Battery |
US10811680B2 (en) * | 2014-07-04 | 2020-10-20 | Enocell Limited | Battery |
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US10531555B1 (en) * | 2016-03-22 | 2020-01-07 | The United States Of America As Represented By The Secretary Of The Army | Tungsten oxide thermal shield |
US11908995B2 (en) | 2017-11-02 | 2024-02-20 | Taiyo Yuden Co., Ltd. | All solid battery |
US11870057B2 (en) * | 2018-02-06 | 2024-01-09 | Navitas Systems, Llc | Dry process formation of solid state lithium ion cell |
US10910619B2 (en) | 2018-04-25 | 2021-02-02 | Samsung Electronics Co., Ltd. | Ion conducting membrane, making method thereof, secondary battery comprising the same |
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Also Published As
Publication number | Publication date |
---|---|
EP0260679A3 (de) | 1991-01-02 |
CN87107102A (zh) | 1988-06-15 |
CN1022273C (zh) | 1993-09-29 |
EP0260679B1 (de) | 1993-05-19 |
DE3785901D1 (de) | 1993-06-24 |
CA1309456C (en) | 1992-10-27 |
KR900007731B1 (ko) | 1990-10-19 |
EP0260679A2 (de) | 1988-03-23 |
KR880004595A (ko) | 1988-06-07 |
DE3785901T2 (de) | 1993-12-16 |
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